Aromatic dicyanate compounds with high aliphatic carbon content

ABSTRACT

Aromatic dicyanate compounds which comprise aliphatic moieties having at least about six carbon atoms and resins and thermoset products based on these compounds.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to aromatic dicyanate compoundswhich comprise aliphatic moieties having at least about six carbon atomsand to resins and thermoset products based on these compounds.

2. Discussion of Background Information

The performance requirements for thermosetting resins used in electricalapplications continue to escalate. In particular, high frequencyelectronics have become more commonplace with advances in computer,communications, and wireless technologies. In view thereof, there is aneed for resins which show reduced dielectric constants and dissipationfactors as well as enhanced thermal resistance.

Aromatic cyanate compounds have been used in electronics applicationsfor many years. The most common cyanate, bisphenol A dicyanate of thefollowing formula:

can be prepared by reaction of bisphenol A (isopropylidene diphenol)with a cyanogen halide, for example, cyanogen bromide, in the presenceof an acid acceptor, for example, triethylamine. Another known aromaticdicyanate compound is the dicyanate of cyclohexanone bisphenol. See,e.g., EP 612 783, the entire disclosure whereof is expresslyincorporated by reference herein.

SUMMARY OF THE INVENTION

It has now been found that the dielectric properties of resins producedfrom aromatic cyanate compounds can be improved by increasing thehydrocarbon content of the cyanate compound.

Specifically, the present inventors have found, inter alfa, a class ofaromatic dicyanate compounds which contain a high percentage ofnon-polar hydrocarbon groups and afford resins with an improvedcombination of (low) dielectric constants and dissipation factors, alongwith a high glass transition temperature Tg. While it was speculatedthat the incorporation of a large hydrocarbon structure would bedeleterious to the thermal properties and the cure profile of athermosettable mixture incorporating these dicyanate compounds, theexact opposite was observed (see Examples below). Thus, the hydrocarbonportion of the aromatic dicyanate compounds was found to be desirablebecause it affords enhanced thermal resistance, low moisture absorptionand excellent dielectric properties, without a deleterious effect on thecure behavior of a thermosettable mixture prepared therefrom or the Tgof cured products made therefrom. It was unexpectedly found that theincreased hydrocarbon content of the aromatic dicyanate compounds of thepresent invention can moderate the enthalpic cure energy withoutincreasing the cure onset and end temperatures. This reduction inexothermicity on cure can help to prevent damage such as cracking ordelamination which may result from the cure of dicyanates which comprisea smaller proportion of non-polar hydrocarbon groups than the dicyanatesof the present invention.

The present invention provides aromatic dicyanate compounds of formula(I):

wherein:

-   each m independently is 0, 1, or 2;-   the moieties R^(a) and R^(b) independently represent optionally    substituted aliphatic groups having a total of from about 5 to about    24 carbon atoms and R^(a) and R^(b) together with the carbon atom to    which they are bonded may form an optionally substituted and/or    optionally unsaturated and/or optionally polycyclic aliphatic ring    structure which has at least about 8 ring carbon atoms; and-   the moieties R independently represent halogen, cyano, nitro,    optionally substituted alkyl, optionally substituted cycloalkyl,    optionally substituted alkoxy, optionally substituted alkenyl,    optionally substituted alkenyloxy, optionally substituted aryl    having from 6 to about 10 carbon atoms, optionally substituted    aralkyl having from 7 to about 12 carbon atoms, optionally    substituted aryloxy having from 6 to about 10 carbon atoms, and    optionally substituted aralkoxy having from 7 to about 12 carbon    atoms.

In one aspect, the aromatic dicyanate compounds of formula (I) may bearomatic dicyanate compounds of formula (Ia):

wherein:

-   n has a value of from about 7 to about 24;-   each m independently is 0, 1, or 2; and-   the moieties R independently represent halogen, cyano (—CN), nitro,    unsubstituted or substituted alkyl preferably having from 1 to about    6 carbon atoms, unsubstituted or substituted cycloalkyl preferably    having from about 5 to about 8 carbon atoms, unsubstituted or    substituted alkoxy preferably having from 1 to about 6 carbon atoms,    unsubstituted or substituted alkenyl preferably having from 3 to    about 6 carbon atoms, unsubstituted or substituted alkenyloxy    preferably having from 3 to about 6 carbon atoms, unsubstituted or    substituted aryl preferably having from 6 to about 10 carbon atoms,    unsubstituted or substituted aralkyl preferably having from 7 to    about 12 carbon atoms, unsubstituted or substituted aryloxy    preferably having from 6 to about 10 carbon atoms, and unsubstituted    or substituted aralkoxy preferably having from 7 to about 12 carbon    atoms;-   and any non-aromatic cyclic moieties comprised in the above formula    (Ia) may optionally carry one or more substituents and/or may    optionally comprise one or more double bonds and/or may optionally    be polycyclic (e.g., bicyclic or tricyclic).

In one aspect of the aromatic dicyanate compounds of formula (Ia), n mayhave a value of from about 9 to about 16; for example, n may have avalue of 9, 10, or 11 and may in particular equal 11.

In one aspect of the compounds of formula (I)/(Ia), each m mayindependently be 0 or 1.

Non-limiting examples of the dicyanates of formula (I)/(Ia) include1,1-bis(4-cyanatophenyl)cyclododecane,1,1-bis(4-cyanato-3,5-dimethylphenyl)cyclododecane,1,1-bis(4-cyanato-3-methylphenyl)cyclododecane,1,1-bis(4-cyanatophenyl)cyclodecane, 2,2-bis(4-cyanatophenyl)adamantane,4,4′-bis(4-cyanatophenyl)octahydro-1,4:5,8-dimethanonaphthalen-2(1H)ylideneand 5,5-bis(4-cyanatophenyl)hexahydro-4,7-methanoindane. A preferredexample of the compounds of formula (I)/(Ia) is1,1-bis(4-cyanatophenyl)cyclododecane.

The present invention also provides polymers (i.e., homo- andcopolymers) and prepolymers of the dicyanate compounds of formula (I)set forth above (including the various aspects thereof).

The present invention also provides a first polymerizable mixture whichcomprises at least one aromatic dicyanate compound of the presentinvention as set forth above (including the various aspects thereof)and/or a prepolymer thereof and one or more substances which areselected from polymerization catalysts, co-curing agents, flameretardants, synergists for flame retardants, solvents, fillers, adhesionpromoters, wetting aids, dispersing aids, surface modifiers,thermoplastic polymers, and mold release agents.

The present invention also provides a second polymerizable mixture whichcomprises (i) at least one aromatic dicyanate compound of the presentinvention as set forth above (including the various aspects thereof)and/or a prepolymer thereof and (ii) at least one compound and/or aprepolymer thereof which is capable of reacting with (i).

In one aspect of the second mixture, the at least one compound (ii) maybe selected from compounds which comprise one or more polymerizableethylenically unsaturated moieties, aromatic di- and polycyanates whichare different from a dicyanate of formula (I), aromatic di- andpolycyanamides, di- and polymaleimides, and di- and polyglycidyl ethers.

In another aspect, the second mixture may further comprise one or moresubstances which are selected from polymerization catalysts, co-curingagents, flame retardants, synergists for flame retardants, solvents,fillers, adhesion promoters, wetting aids, dispersing aids, surfacemodifiers, thermoplastic polymers, and mold release agents.

In another aspect, each of the above first and second mixtures may bepartially or completely polymerized and the present invention alsoprovides a product which comprises such a polymerized mixture.

In one aspect, the product may comprise at least one of an electricallaminate, an IC (integrated circuit) substrate, a casting, a coating, adie attach and mold compound formulation, a composite, and an adhesive.

The present invention also provides a process for preparing a dicyanatecompound of the present invention as set forth above (including thevarious aspects thereof). The process comprises the reaction a compoundof formula (II):

wherein m, R^(a), R^(b) and R are as set forth above with respect toformula (I), in a solvent with an at least about stoichiometric quantityof a cyanogen halide in the presence of an at least about stoichiometricquantity of a base.

In one aspect of the process, the cyanogen halide may comprise cyanogenchloride and/or cyanogen bromide.

In another aspect, the reaction may be carried out at a temperature offrom about −40° C. to about 60° C.

In yet another aspect of the process of the present invention, the basemay comprise one or more of sodium hydroxide, potassium hydroxide,trimethylamine, and triethylamine and in particular, triethylamine.

In a still further aspect of the process, the solvent may comprise oneor more of water, an aliphatic ketone, a chlorinated hydrocarbon, analiphatic or cycloaliphatic ether or diether, and an aromatichydrocarbon. For example, the solvent may comprise one or more ofacetone, methylethylketone, methylene chloride, and chloroform.

Other features and advantages of the present invention will be set forthin the description of invention that follows, and will be apparent, inpart, from the description or may be learned by practice of theinvention. The invention will be realized and attained by thecompositions, products, and methods particularly pointed out in thewritten description and claims hereof.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

Unless otherwise stated, a reference to a compound or component includesthe compound or component by itself, as well as in combination withother compounds or components, such as mixtures of compounds.

As used herein, the singular forms “a,” “an,” and “the” include theplural reference unless the context clearly dictates otherwise.

Except where otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. Atthe very least, and not to be considered as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding conventions.

Additionally, the recitation of numerical ranges within thisspecification is considered to be a disclosure of all numerical valuesand ranges within that range. For example, if a range is from about 1 toabout 50, it is deemed to include, for example, 1, 7, 34, 46.1, 23.7, orany other value or range within the range.

The particulars shown herein are by way of example and for purposes ofillustrative discussion of the embodiments of the present invention onlyand are presented in the cause of providing what is believed to be themost useful and readily understood description of the principles andconceptual aspects of the present invention. In this regard, no attemptis made to show embodiments of the present invention in more detail thanis necessary for the fundamental understanding of the present invention,the description making apparent to those skilled in the art how theseveral forms of the present invention may be embodied in practice.

As set forth above, the present invention provides, inter alfa, aromaticdicyanate compounds of formula (I):

The moieties R^(a) and R^(b) in the above formula may independentlyrepresent optionally substituted aliphatic groups having a total of fromabout 5 to about 24 carbon atoms. Usually, the total number of carbonatoms in the aliphatic moieties R^(a) and R^(b) will be at least about6, e.g., at least about 7, at least about 8, at least about 9, or atleast about 10, but will usually be not higher than about 18, e.g., nothigher than about 16, or not higher than about 14. The aliphaticmoieties may be linear, branched or cyclic and saturated or unsaturated.Non-limiting examples thereof are linear or branched alkyl groups andalkenyl groups, cycloalkyl and cycloalkenyl groups as well asalkylcycloalkyl and cycloalkylalkyl groups such as, e.g., methyl, ethyl,n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, cyclohexyl, methylcyclohexyl,and cyclohexylmethyl, and the corresponding mono- and diunsaturatedgroups. Further, these groups may be substituted by one or more (e.g.,1, 2, 3, or 4) substituents. Non-limiting examples of substituents areF, Cl and Br as well as aromatic groups (such as, e.g., phenyl). Also,often one of the moieties R^(a) and R^(b) will represent methyl orethyl, in particular, methyl.

The moieties R^(a) and R^(b) in the above formula (I) may also form,together with the carbon atom to which they are bonded, an optionallysubstituted and/or optionally polycyclic aliphatic ring structure whichhas at least about 8 ring carbon atoms. Examples of correspondingcompounds are those of formula (Ia):

The value of n in the above formula (Ia) is not lower than about 7,e.g., not lower than about 8, not lower than about 9, or not lower thanabout 10, and not higher than about 24, e.g., not higher than about 16,not higher than about 14, or not higher than about 12, and preferablyequals 8, 9, 10, 11, or 12, in particular 11 (i.e., giving rise to acyclododecylidene structure).

The cycloaliphatic moiety shown in the above formula (Ia) may optionallybe polycyclic (e.g., bicyclic or tricyclic) and/or may optionallycomprise one or more (e.g., 1, 2, 3, or 4) double bonds and/or mayoptionally carry one or more (e.g., 1, 2, or 3) substituents. If morethan one substituent is present, the substituents may be the same ordifferent. Non-limiting examples of substituents which may be present onthe cycloaliphatic moiety include alkyl groups, e.g., optionallysubstituted alkyl groups having from 1 to about 6 carbon atoms (e.g.,methyl or ethyl), and halogen atoms such as, e.g., F, Cl, and Br. Thealkyl groups may be substituted with, for example, one or more halogenatoms such as, e.g., F, Cl, and Br.

The value of each m in the above formula (I)/(Ia) independently is 0, 1or 2. Preferably, the values of m are identical and/or are 0 or 1.

The moieties R in the above formula (I)/(Ia) independently representhalogen (e.g., F, Cl, and Br, preferably Cl or Br), cyano, nitro,unsubstituted or substituted alkyl preferably having from 1 to about 6carbon atoms, unsubstituted or substituted cycloalkyl preferably havingfrom about 5 to about 8 carbon atoms, unsubstituted or substitutedalkoxy preferably having from 1 to about 6 carbon atoms, unsubstitutedor substituted alkenyl preferably having from 3 to about 6 carbon atoms,unsubstituted or substituted alkenyloxy preferably having from 3 toabout 6 carbon atoms, unsubstituted or substituted aryl preferablyhaving from 6 to about 10 carbon atoms, unsubstituted or substitutedaralkyl preferably having from 7 to about 12 carbon atoms, unsubstitutedor substituted aryloxy preferably having from 6 to about 10 carbonatoms, and unsubstituted or substituted aralkoxy preferably having from7 to about 12 carbon atoms.

It is to be appreciated that whenever the terms “alkyl” and “alkenyl”are used in the present specification and the appended claims, theseterms also include the corresponding cycloaliphatic groups such as,e.g., cyclopentyl, cyclohexyl, cyclopentenyl, and cyclohexenyl. Also,where two alkyl and/or alkenyl groups are attached to two (preferablyadjacent) carbon atoms of an aliphatic or aromatic ring, they may becombined to form an alkylene or alkenylene group which together with thecarbon atoms to which this group is attached results in a preferably 5-or 6-membered ring structure. In the case of non-adjacent carbon atoms,this ring structure may give rise to a bicyclic compound.

The above alkyl groups and alkoxy groups R will often comprise from 1 toabout 4 carbon atoms and in particular, 1 or 2 carbon atoms.Non-limiting specific examples of these groups include, methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl andmethoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,and tert-butoxy. The alkyl and alkoxy groups may be substituted with oneor more (e.g., 1, 2, or 3) substituents. If more than one substituent ispresent, the substituents may be the same or different and arepreferably identical. Non-limiting examples of these substituentsinclude halogen atoms such as, e.g., F, Cl, and Br. Non-limitingspecific examples of substituted alkyl and alkoxy groups include CF₃,CF₃CH₂, CCl₃, CCl₃CH₂, CHCl₂, CH₂Cl, CH₂Br, CCl₃O, CHCl₂O, CH₂ClO, andCH₂BrO.

The above alkenyl and alkenyloxy groups will often comprise 3 or 4carbon atoms and in particular, 3 carbon atoms. Non-limiting specificexamples of these groups are allyl, methallyl, and 1-propenyl. Thealkenyl and alkenyloxy groups may be substituted with one or more (e.g.,1, 2, or 3) substituents. If more than one substituent is present, thesubstituents may be the same or different and are preferably identical.Non-limiting examples of these substituents include halogen atoms suchas, e.g., F, Cl, and Br.

The above aryl and aryloxy groups will often be phenyl and phenoxygroups. The aryl and aryloxy groups may be substituted with one or more(e.g., 1, 2, 3, 4, or 5) substituents. If more than one substituent ispresent, the substituents may be the same or different. Non-limitingexamples of these substituents include nitro, cyano, halogen such as,e.g., F, Cl, and Br, optionally halogen-substituted alkyl having from 1to about 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (forexample, methyl or ethyl) and optionally halogen-substituted alkoxyhaving from 1 to about 6 carbon atoms, e.g., from 1 to about 4 carbonatoms (for example, methoxy or ethoxy). Non-limiting specific examplesof substituted aryl and aryloxy groups include but are not limited to,tolyl, xylyl, ethylphenyl, chlorophenyl, bromophenyl, tolyloxy,xylyloxy, ethylphenoxy, chlorophenoxy, and bromophenoxy.

The above aralkyl and aralkoxy groups will often be benzyl, phenethyl,benzyloxy, or phenethoxy groups. These groups may be substituted(preferably on the aryl ring, if at all) with one or more (e.g., 1, 2,3, 4, or 5) substituents. If more than one substituent is present, thesubstituents may be the same or different. Non-limiting examples ofthese substituents include nitro, cyano, halogen such as, e.g., F, Cl,and Br, optionally halogen-substituted alkyl having from 1 to about 6carbon atoms, e.g., from 1 to about 4 carbon atoms (for example, methyl,or ethyl) and optionally halogen-substituted alkoxy having from 1 toabout 6 carbon atoms, e.g., from 1 to about 4 carbon atoms (for example,methoxy, or ethoxy).

The dicyanates of formula (I)/(Ia) may be prepared by methods which arewell known to those of skill in the art. For example, the dicyanates maybe prepared by reaction of a corresponding bisphenol with a cyanogenhalide. The bisphenols can be prepared, for example, by condensation ofphenols with ketones using methods well known in the art. Examples ofthese methods are described in, e.g., U.S. Pat. No. 4,438,241 and DE3345945, the entire disclosures whereof are incorporated by referenceherein. Generally speaking, the ketone is treated with a large excess ofa phenol in the presence of an acid catalyst, non-limiting examples ofwhich include mineral acids such as HCl or H₂SO₄, arylsulfonates, oxalicacid, formic acid, or acetic acid. A cocatalyst such as, e.g., amercaptan may be added. Rather than using a soluble acid catalyst, it isalso common to use a bed of sulfonated crosslinked polystyrene beads.Non-limiting examples of suitable ketone starting materials includecycloaliphatic ketones such as, e.g., cyclododecanone, cyclodecanone,adamantanone and other ketones derived from polycyclic hydrocarbons aswell as aliphatic ketones such as, e.g., 2-octanone, 3-octanone,2-nonanone, 3-nonanone, 2,4,8-trimethyl-4-nonanone, 2-decanone,3-decanone, 2-undecanone, 6-undecanone, 2-methyl-4-undecanone,2-dodecanone, 3-dodecanone and 4-dodecanone. Non-limiting examples ofsuitable phenol starting materials include phenol, o-cresol, m-cresol,p-cresol, o-chlorophenol, o-bromophenol, 2-ethylphenol, 2-octylphenol,2-nonylphenol, 2,6-xylenol, 2-t-butyl-5-methylphenol,2-t-butyl-4-methylphenol, 2,4-di(t-butyl)phenol, 2-t-butylphenol,2-sec-butylphenol, 2-n-butylphenol, 2-cyclohexylphenol,4-cyclohexylphenol, 2-cyclohexyl-5-methylphenol, α-decalone, andβ-decalone.

It is well known in the art that this condensation chemistry can give amixture of products such as o-alkylation of the phenol, oligomersderived from multiple alkylation of the phenol by the ketone, andacid-catalyzed rearrangement products. These impurities can either beremoved or left in the material used as starting material for thecyanation reaction. In some regards these impurities can be beneficial,in that they lower the melting point of the final cyanated product. Thiscan make it easier to prepare to formulate the cyanate by making it moresoluble and reducing the tendency to crystallize The presence of theoligomers tends to increase the viscosity of the cyanate and thereforeits formulated products. This can be a beneficial or harmful propertydepending on the application.

By way of non-limiting example, the dicyanate compounds, such as1,1-bis(4-cyanatophenyl)cyclododecane, may be prepared by reacting acycloalkane bisphenol, such as 1,1-bis(4-hydroxyphenyl)cyclododecane,with an about stoichiometric quantity or a slight stoichiometric excess(up to about 20 percent excess) of a cyanogen halide per phenolichydroxyl group in the presence of an about stoichiometric quantity or aslight stoichiometric excess (up to about 20 percent excess) of a basecompound per phenolic hydroxyl group and in the presence of a suitablesolvent. This reaction may schematically be represented as follows (forthe case of 1,1-bis(4-cyanatophenyl)cyclododecane):

Usually reaction temperatures of from about −40° C. to about 60° C. areemployed, with reaction temperatures of from about −15° C. to about 10°C. being preferred and reaction temperatures of from about −10° C. toabout 0° C. being particularly preferred. Reaction times can varysubstantially, for example, as a function of the reactants beingemployed, the reaction temperature, solvent(s) used, the scale of thereaction, and the like, but are often in the range of from about 15minutes to about 4 hours, with reaction times of from about 30 minutesto about 90 minutes being preferred.

Non-limiting examples of suitable cyanogen halides include cyanogenchloride and cyanogen bromide. Alternately, the method of Martin andBauer described in Organic Synthesis, volume 61, pages 35-68 (1983),published by John Wiley and Sons, the entire disclosure of which isexpressly incorporated by reference herein, can be used to generate thecyanogen halide in situ from sodium cyanide and a halogen such aschlorine or bromine.

Non-limiting examples of suitable base compounds for use in the aboveprocess include both inorganic bases and tertiary amines such as sodiumhydroxide, potassium hydroxide, trimethylamine, triethylamine, andmixtures thereof. Triethylamine is most preferred as the base.

Non-limiting examples of suitable solvents for the cyanation reactioninclude water, aliphatic ketones, chlorinated hydrocarbons, aliphaticand cycloaliphatic ethers and diethers, aromatic hydrocarbons, andmixtures thereof. Acetone, methylethylketone, methylene chloride, andchloroform are particularly suitable as the solvent.

The aromatic dicyanate compounds of the present invention can usually becured (thermoset) by heating at a temperature of from about 50° C. toabout 400° C., preferably by heating at a temperature of from about 100°C. to about 250° C., optionally in the presence of a suitable catalyst.

Examples of suitable catalysts include acids, bases, salts, nitrogen andphosphorus compounds, such as for example, Lewis acids such as, e.g.,AlCl₃, BF₃, FeCl₃, TiCl₄, ZnCl₂and SnCl₄; protonic acids such as HCl,and H₃PO₄; aromatic hydroxy compounds such as phenol, p-nitrophenol,pyrocatechol, dihydroxynaphthalene; sodium hydroxide, sodium methylate,sodium phenolate, trimethylamine, triethylamine, tributylamine,diazabicyclo [2.2.2]octane, quinoline, isoquinoline,tetrahydroisoquinoline, tetraethylammonium chloride, pyridine-N-oxide,tributyl phosphine, zinc octoate, tin octoate, zinc naphthenate, cobaltnaphthenate, cobalt octoate, cobalt acetylacetonate and the like. Alsosuitable as catalysts are metal chelates such as, for example, thechelates of transition metals and bidentate or tridentate ligands,particularly the chelates of iron, cobalt, zinc, copper, manganese,zirconium, titanium, vanadium, aluminum, and magnesium. These and othercatalysts are disclosed in U.S. Pat. Nos. 3,694,410 and 4,094,852, theentire disclosures whereof are incorporated by reference herein. Cobaltnaphthenate, cobalt octoate, and cobalt acetylacetonate are particularlysuitable as the catalysts.

The quantity of catalyst(s) used, if any, may depend on the structure ofthe particular catalyst(s), the structure of the dicyanate compoundbeing cured, the cure temperature, the cure time, and the like.Generally, catalyst concentrations of from about 0.001 to about 2percent by weight, based on the total weight of the polymerizablecomponents, are preferred.

B-staging or prepolymerization of the dicyanate compounds of the presentinvention can be accomplished by using lower temperatures and/or shortercuring times than those set forth above. Curing of a thus formedB-staged (prepolymerized) resin can then be accomplished at a later timeor immediately following B-staging (prepolymerization) by increasing thetemperature and/or the cure time.

The cured (thermoset) products prepared from the dicyanate compounds ofthe present invention comprise the cyanate group homopolymerizationstructure, i.e., the 1,3,5-triazine ring, unless other functionalitiesare present in the curable mixture that participate in the curingprocess and prevent a formation of the 1,3,5-triazine ring structure.

The aromatic dicyanate compounds of the present invention may becopolymerized with a variety of other compounds and/or prepolymersthereof. In corresponding copolymerizable mixtures, one or moredicyanates of formula (I)/(Ia) and/or prepolymers thereof may, forexample, be present in quantities of from about 5% to about 95% byweight, e.g., from about 10% to about 90% by weight or from about 25% toabout 75% by weight, based on the total weight of the polymerizablecomponents.

Non-limiting examples of compounds (including prepolymers thereof) whichmay be copolymerized with the dicyanates of formula (I) and/orprepolymers thereof include compounds which comprise one or morepolymerizable ethylenically unsaturated moieties, aromatic di- andpolycyanates which are different from the dicyanates of formula (I),aromatic di- and polycyanamides, di- and polymaleimides, and di- andpolyglycidyl ethers (epoxy resins) such as, e.g., diglycidyl ethers ofbisphenol A or bisphenol F, polyglycidyl ethers of phenol novolac orcresol novolac resins and the epoxy resins disclosed in the co-assignedapplication entitled “POLYPHENOLIC COMPOUNDS AND EPOXY RESINS COMPRISINGCYLCOALIPHATIC MOIETIES AND PROCESS FOR THE PRODUCTION THEREOF”, filedconcurrently herewith (Attorney Docket No. 65221), the entire disclosurewhereof is expressly incorporated by reference herein.

Of course, it is also possible to copolymerize the aromatic dicyanatecompounds of the present invention and/or prepolymers thereof with othercomponents such as, e.g., one or more of (a) at least one compound whichcontains in the same molecule both a cyanate or cyanamide group and apolymerizable ethylenically unsaturated group; (b) at least one compoundwhich contains in the same molecule both a 1,2-epoxide group and apolymerizable ethylenically unsaturated group; (c) at least one compoundwhich contains in the same molecule both a maleimide group and a cyanategroup; (d) at least one polyamine; and (e) at least one polyphenol, etc.Non-limiting specific examples of the use of dicyanates for makingformulations which contain bismaleimides and epoxy resins and are usefulfor the production of high performance electrical laminates aredisclosed in, e.g., U.S. Pat. No. 4,110,364, the entire disclosurewhereof is incorporated herein by reference.

Specific and non-limiting examples of compounds (including prepolymersthereof) which may be copolymerized with the dicyanates of formula(I)/(Ia) include compounds of formula (III) and prepolymers thereof:

wherein:

-   n has a value of from about 5 to about 24;-   each m independently is 0, 1, or 2;-   the moieties R independently represent halogen, cyano, nitro,    hydroxy, amino optionally carrying one or two alkyl groups    preferably having from 1 to about 6 carbon atoms, unsubstituted or    substituted alkyl preferably having from 1 to about 6 carbon atoms,    unsubstituted or substituted cycloalkyl preferably having from about    5 to about 8 carbon atoms, unsubstituted or substituted alkoxy    preferably having from 1 to about 6 carbon atoms, unsubstituted or    substituted alkenyl preferably having from 3 to about 6 carbon    atoms, unsubstituted or substituted alkenyloxy preferably having    from 3 to about 6 carbon atoms, unsubstituted or substituted aryl    preferably having from 6 to about 10 carbon atoms, unsubstituted or    substituted aralkyl preferably having from 7 to about 12 carbon    atoms, unsubstituted or substituted aryloxy preferably having from 6    to about 10 carbon atoms, and unsubstituted or substituted aralkoxy    preferably having from 7 to about 12 carbon atoms; and-   the moieties Q independently represent hydrogen, cyano,    HR¹C═CR¹—CH₂—, or H₂R¹C—CR¹═HC— wherein the moieties R¹    independently represent hydrogen or unsubstituted or substituted    alkyl having from 1 to about 3 carbon atoms;-   with the provisos that (1) when both moieties Q are hydrogen, at    least one moiety R represents HR¹C═CR¹—CH₂— or H₂R¹C—CR¹═HC—, (2)    not more than one group Q represents cyano and (3) any non-aromatic    cyclic moieties comprised in the above formula (III) may optionally    carry one or more substituents and/or may optionally comprise one or    more double bonds and/or may optionally be polycyclic (e.g.,    bicyclic or tricyclic).

Regarding the cycloaliphatic moiety shown in formula (III) and themeanings of n, m and R in formula (III) the comments set forth abovewith respect to the compounds of formula (I)/(Ia) apply in theirtotality.

The moieties Q in the above formula (III) independently representhydrogen, cyano, HR¹C═CR¹—CH₂— or H₂R¹C—CR¹═HC— wherein the moieties R¹independently represent hydrogen or unsubstituted or substituted(preferably unsubstituted) alkyl having from 1 to about 3 carbon atoms.A preferred moiety Q is allyl. Also, it is preferred for the moieties Qto be identical and to represent HR¹C═CR¹—CH₂— or H₂R¹C—CR¹═HC— and/orto be different from hydrogen. Also preferably, at least one of themoieties Q is not hydrogen.

Non-limiting specific examples of the above alkyl moieties R¹ includemethyl, ethyl, propyl, and isopropyl. Methyl is preferred. If one ormore substituents are present on these alkyl groups they may, forexample, be halogen such as, e.g., F, Cl, and Br.

Non-limiting examples of the above compounds of formula (III) include1,1-bis(4-hydroxyphenyl)cyclododecane bis(allyl ether),1,1-bis(4-hydroxyphenyl)-cyclododecane bis(methallyl ether),1,1-bis(4-hydroxyphenyl)-cyclododecane bis(1-propenyl ether),1,1-bis(4-hydroxyphenyl)cyclodecane bis(allyl ether),1,1-bis(4-hydroxyphenyl)cyclodecane bis(methallyl ether),1,1-bis(4-hydroxyphenyl)-cyclodecane bis(1-propenyl ether),2,2-bis(4-hydroxyphenyl)adamantane bis(allyl ether),2,2-bis(4-hydroxyphenyl)adamantane bis(methallyl ether),4,4′-bis(4-hydroxyphenyl)octahydro-1,4:5,8-dimethanonaphthalen-2(1H)ylidenebis(allyl ether),4,4′-bis(4-hydroxyphenyl)octahydro-1,4:5,8-dimethanonaphthalen-2(1H)ylidenebis(methallyl ether),5,5-bis(4-hydroxyphenyl)hexahydro-4,7-methanoindane bis(allyl ether) and5,5-bis(4-hydroxyphenyl)hexahydro-4,7-methanoindane bis(methallylether).

Further non-limiting examples of the above compounds of formula (III)include partial or complete Claisen rearrangement products of compoundsof formula (III) wherein at least one of the moieties Q representsHR¹C═CR¹—CH₂— or H₂R¹C—CR¹═HC—, as well as monomers which carry at leastone substituent on at least one aromatic ring to block a Claisenrearrangement.

The compounds of formula (III) may prepared by methods which are wellknown to those of skill in the art. For example, these monomers may beprepared by etherification of a cycloalkane bisphenol of the aboveformula (II) with a compound which comprises a group HR¹C═CR¹—CH₂— orH₂R¹C—CR¹═HC—. In this regard, reference may also be made to theco-assigned application entitled “ETHYLENICALLY UNSATURATED MONOMERSCOMPRISING ALIPHATIC AND AROMATIC MOIETIES”, filed concurrently herewith(Attorney Docket No. 66641), the entire disclosure of which is expresslyincorporated by reference herein.

By way of non-limiting example, the allylation of a bisphenol of formula(II) may be accomplished via a transcarbonation reaction using, forexample, allyl methyl carbonate, or a direct allylation reaction using,for example, an allyl halide, a methallyl halide and the like plus analkaline agent and optional catalyst such as a phase transfer catalyst.

A direct allylation reaction of the bisphenol of the above formula (II)with an allyl halide such as allyl chloride may, for example, beconducted in the presence of an alkaline agent such as an aqueoussolution of an alkali metal hydroxide (e.g., NaOH). If desired, inertsolvents such as, e.g., 1,4-dioxane and phase transfer catalysts suchas, e.g., benzyltrialkylammonium halides or tetraalkylammonium halidescan be employed.

Further specific and non-limiting examples of compounds (includingprepolymers thereof) which may be copolymerized with the aromaticdicyanates of formula (I)/(Ia) include compounds of formula (IV) andprepolymers thereof:

wherein:

-   p is 0 or an integer of from 1 to about 19;-   each m independently is 0, 1, or 2;-   the moieties R independently represent halogen, cyano, nitro,    unsubstituted or substituted alkyl preferably having from 1 to about    6 carbon atoms, unsubstituted or substituted alkoxy preferably    having from 1 to about 6 carbon atoms, unsubstituted or substituted    alkenyl preferably having from 3 to about 6 carbon atoms,    unsubstituted or substituted alkenyloxy preferably having from 3 to    about 6 carbon atoms, unsubstituted or substituted aryl preferably    having from 6 to about 10 carbon atoms, unsubstituted or substituted    aralkyl preferably having from 7 to about 12 carbon atoms,    unsubstituted or substituted aryloxy preferably having from 6 to    about 10 carbon atoms, and unsubstituted or substituted aralkoxy    preferably having from 7 to about 12 carbon atoms; and-   the moieties Q independently represent hydrogen, cyano,    HR¹C═CR¹—CH₂—, or H₂R¹C—CR¹═HC— wherein the moieties R¹    independently represent hydrogen or unsubstituted or substituted    alkyl having from 1 to about 3 carbon atoms;-   with the proviso that when all four moieties Q are hydrogen, at    least one moiety R represents HR¹C═CR¹—CH₂— or H₂R¹C—CR¹═HC—;

and any non-aromatic cyclic moieties comprised in the above formula (IV)may optionally carry one or more substituents and/or may optionallycomprise one or more double bonds.

In the above formula (IV), p is 0 or an integer of from 1 to about 19,e.g., up to about 14, up to about 12 or up to about 8 such as, e.g., 1,2, 3, 4, 5, 6, and 7, with 1, 2, or 3 being preferred and 1 beingparticularly preferred. Regarding exemplary and preferred meanings of n,R, Q and R¹ in formula (IV) the comments with respect to the aboveformulae (I) and (III) apply in their entirety and are expresslyreferred to.

Non-limiting specific examples of the above compounds of formula (IV)include (for Q=HR¹C═CR¹—CH₂— or H₂R¹C—CR¹═HC—) dimethylcyclohexanetetraphenol tetra(allyl ether), dimethylcyclohexane tetraphenoltetra(methallyl ether), dimethylcyclohexane tetraphenol tetra(1-propenylether), dimethylcyclooctane tetraphenol tetra(allyl ether),dimethylcyclooctane tetraphenol tetra(methallyl ether),dimethylcyclooctane tetraphenol tetra(1-propenyl ether), partial orcomplete Claisen rearrangement products of dimethylcyclohexanetetraphenol tetra(allyl ether), and compounds which carry at least onesubstituent on at least one aromatic ring to block a Claisenrearrangement. Non-limiting specific examples of the above compounds offormula (IV) further include (for Q=-CN) dimethylcyclohexane tetraphenoltetracyanate, and dimethylcyclooctane tetraphenol tetracyanate.

The compounds of the above formula (IV) may be prepared, for example, bya process which comprises the condensation of a dialdehyde of acorresponding cycloalkane, which comprises from about 5 to about 24 ringcarbon atoms, with a corresponding hydroxyaromatic (e.g., phenolic)compound (such as, e.g., phenol) at a molar ratio of aromatic hydroxygroups to aldehyde groups, which affords a mixture of polyphenoliccompounds with a polydispersity (Mw/Mn) of not higher than about 2,e.g., not higher than about 1.8, or not higher than about 1.5, andoptionally subjecting the mixture of polyphenolic compounds to anetherification reaction and/or cyanation reaction (e.g., with a cyanogenhalide, see above) to partially or completely convert the phenolicgroups which are present in the mixture into cyanate groups (—OCN)and/or into ether groups of formula HR¹C═CR¹—CH₂—O— and/orH₂R¹C—CR¹═HC—O— wherein the moieties R¹ independently represent hydrogenor unsubstituted or substituted alkyl having from 1 to about 3 carbonatoms. This process affords the compounds of formula (IV) in admixturewith other monomers of similar structure but with higher (and lower)molecular weights (higher or lower degree of condensation).

The cycloaliphatic dialdehydes which are starting materials for theabove process may be prepared by methods which are well known to thoseof skill in the art. By way of non-limiting example, cyclohexanedialdehyde can be produced by a hydroformylation of cyclohex-3-enecarboxaldehyde. This process produces a mixture of 1,3- and1,4-cyclohexane dicarboxaldehydes. Condensation of this mixture ofdialdehydes with phenol affords a novolac which comprises cyclohexanedialdehyde tetraphenol along with compounds with a higher and lowerdegree of condensation. The process renders it possible to produce verylow polydispersity products with a high average functionality. Forexample, when using phenol and cyclohexane dialdehyde as startingmaterials, products having a weight average molecular weight (Mw) ofabout 930 and a number average molecular weight (Mn) of about 730 and/oran average of about 6 hydroxy groups per molecule can routinely beproduced. The process preferably uses a relatively high molar ratio ofaromatic hydroxy group to aldehyde group (e.g., about 6:1) to keepoligomerization low. The excess hydroxyaromatic compound may then beremoved, for example, by distillation. In this regard, reference mayalso be made to the co-assigned application entitled “AROMATICPOLYCYANATE COMPOUNDS AND PROCESS FOR THE PRODUCTION THEREOF”, filedconcurrently herewith (Attorney Docket No. 66500), the entire disclosureof which is expressly incorporated by reference herein, as well as theabove-mentioned co-assigned application entitled “POLYPHENOLIC COMPOUNDSAND EPDXY RESINS COMPRISING CYLCOALIPHATIC MOIETIES AND PROCESS FOR THEPRODUCTION THEREOF” (Attorney Docket No. 65221).

By way of non-limiting example, the allylation of a cycloalkanetetraphenol such as, e.g., cyclohexane dialdehyde tetraphenol (andrelated phenolic compounds which may be present in admixture therewith)may be accomplished via a transcarbonation reaction using, for example,allyl methyl carbonate or a direct allylation reaction using, forexample, an allyl halide, a methallyl halide, and the like plus analkaline agent and an optional catalyst such as a phase transfercatalyst. In this regard, the corresponding further comments set forthabove with respect to the allylation of compounds of formula (II) may bereferred to.

The (co)polymerizable mixtures of the present invention and the productsmade therefrom respectively, may further comprise one or more othersubstances such as, e.g., one or more additives which are commonlypresent in polymerizable mixtures and products made therefrom.Non-limiting examples of such additives include polymerizationcatalysts, co-curing agents, flame retardants, synergists for flameretardants, solvents, fillers, glass fibers, adhesion promoters, wettingaids, dispersing aids, surface modifiers, thermoplastic resins, and moldrelease agents.

Non-limiting examples of co-curing agents for use in the presentinvention include dicyandiamide, substituted guanidines, phenolics,amino compounds, benzoxazine, anhydrides, amido amines, and polyamides.

Non-limiting examples of catalysts for use in the present invention (inaddition to those set forth above with respect to the homopolymerizationof the dicyanates of formula (I)) include transition metal complexes,imidazoles, phosphonium salts, phosphonium complexes, tertiary amines,hydrazides, “latent catalysts” such as Ancamine 2441 and K61B (modifiedaliphatic amines available from Air Products), Ajinomoto PN-23 or MY-24,and modified ureas.

Non-limiting examples of flame retardants and synergists for use in thepresent invention include phosphorus containing molecules (DOP—epoxyreaction product), adducts of DOPO(6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide), magnesium hydrate, zincborate and metallocenes.

Non-limiting examples of solvents for use in the present invention (forexample, for improving processability) include acetone, methylethylketone, and Dowanol PMA (propylene glycol methyl ether acetate availablefrom Dow Chemical Company).

Non-limiting examples of fillers for use in the present inventioninclude functional and non-functional particulate fillers with aparticle size range of from about 0.5 nm to about 100 μm. Specificexamples thereof include silica, alumina trihydrate, aluminum oxide,metal oxides, carbon nanotubes, silver flake or powder, carbon black,and graphite.

Non-limiting examples of adhesion promoters for use in the presentinvention include modified organosilanes (epoxidized, methacryl, amino,allyl, etc.), acetylacetonates, sulfur containing molecules, titanates,and zirconates.

Non-limiting examples of wetting and dispersing aids for use in thepresent invention include modified organosilanes such as, e.g., Byk 900series and W 9010, and modified fluorocarbons.

Non-limiting examples of surface modifiers for use in the presentinvention include slip and gloss additives, a number of which areavailable from Byk-Chemie, Germany.

Non-limiting examples of thermoplastic resins for use in the presentinvention include reactive and non-reactive thermoplastic resins suchas, e.g., polyphenylsulfones, polysulfones, polyethersulfones,polyvinylidene fluoride, polyetherimides, polyphthalimides,polybenzimidazoles, acrylics, phenoxy resins, and polyurethanes.

Non-limiting examples of mold release agents for use in the presentinvention include waxes such as, e.g., carnauba wax.

The aromatic dicyanate compounds of the present invention are useful,inter alfa, as thermosettable comonomers for the production of printedcircuit boards and materials for integrated circuit packaging (such asIC substrates). They are especially useful for formulating matrix resinsfor high speed printed circuit boards, integrated circuit packaging, andunderfill adhesives. As a comonomer, they may also be used to adjust theamount of hydrocarbon in a thermoset matrix.

Example 1 Synthesis of 1,1-Bis(4-cyanatophenyl)cyclododecane

A 250 milliliter, three neck, glass, round bottom reactor was chargedwith 1,1-bis(4-hydroxyphenyl)cyclododecane (17.63 grams, 0.10 hydroxylequivalent) and acetone (125 milliliters, 7.09 milliliter per gram ofbisphenol). The reactor was additionally equipped with a condenser(maintained at 0° C.), a thermometer, an overhead nitrogen inlet (1 LPMN₂ used), and magnetic stirring. Stirring commenced to give a solutionat 21.5° C. Cyanogen bromide (11.12 grams, 0.105 mole, 1.05:1 cyanogenbromide:hydroxyl equivalent ratio) was added to the solution andimmediately dissolved therein. A dry ice-acetone bath for cooling wasplaced under the reactor followed cooling and equilibration of thestirred solution at −5° C. Triethylamine (10.17 grams, 0.1005 mole,1.005 triethylamine:hydroxyl equivalent ratio) was added using a syringein aliquots that maintained the reaction temperature at −5 to 0° C. Thetotal addition time for the triethylamine was 30 minutes. Addition ofthe initial aliquot of triethylamine induced haziness in the stirredsolution with further additions inducing formation of a white slurry oftriethylamine hydrobromide.

After 8 minutes of post-reaction at −5 to 0.5° C., high pressure liquidchromatographic (HPLC) analysis of a sample of the reaction productrevealed the presence of 0.68 area percent unreacted1,1-bis(4-hydroxyphenyl)cyclododecane, 4.43 area % monocyanate, and93.98 area % dicyanate, with the balance as 7 minor peaks. After acumulative 45 minutes of postreaction at −5° C. to 0° C., HPLC analysisof a sample of the reaction product revealed the presence of 0.84 areapercent unreacted cyclododecane bisphenol, 5.34 area % monocyanate, and93.51 area % dicyanate, with the balance as one minor peak.

After a cumulative 101 minutes of post-reaction, the product slurry wasadded to a beaker of magnetically stirred deionized water (1.5 liters)providing an aqueous slurry. After 5 minutes of stirring, gravityfiltration of the aqueous slurry through filter paper recovered thewhite powder product. The product from the filter paper was rinsed intoa beaker using deionized water to a total volume of 200 milliliters,followed by the addition of dichloromethane (200 milliliters). Asolution formed in the dichloromethane layer. The mixture was added to aseparatory funnel, thoroughly mixed, allowed to settle, and then thedichloromethane layer recovered, with the aqueous layer discarded towaste. The dichloromethane solution was added back into the separatoryfunnel and extracted with fresh deionized water (200 milliliters) twoadditional times.

The resultant hazy dichloromethane solution was dried over granularanhydrous sodium sulfate (5 grams) to give a clear solution which wasthen passed through a bed of anhydrous sodium sulfate (25 grams)supported on a 60 milliliter, medium fritted glass funnel attached to aside arm vacuum flask. The clear filtrate was rotary evaporated using amaximum oil bath temperature of 50° C. until the vacuum was <3.5 mm Hg.A total of 19.81 grams (98.43% uncorrected, isolated yield) of white,crystalline product was recovered. HPLC analysis of a sample of theproduct revealed the presence of 0.47 area percent unreacted1,1-bis(4-hydroxyphenyl)cyclododecane, 3.09 area % monocyanate, and96.44 area % dicyanate.

Example 2 Synthesis of the Homopolytriazine of the1,1-Bis(4-cyanatophenyl)cyclododecane

Differential scanning calorimetry (DSC) analysis of a portion (9.8milligrams) of 1,1-bis(4-cyanatophenyl)cyclododecane from Example 1above was completed using a rate of heating of 7° C. per minute from 25°C. to 400° C. under a stream of nitrogen flowing at 35 cubic centimetersper minute. A single melt endotherm was detected with a 120.8° C. onset,a 129.6° C. midpoint, and a 136.0° C. end, accompanied by an enthalpy of4.5 joules per gram. A single exotherm attributed to cyclotrimerizationwas detected with a 194.8° C. onset, a 289.4° C. midpoint, and a 340.3°C. end, accompanied by an enthalpy of 562.3 joules per gram. A secondscanning of the resultant homopolytriazine revealed a weak transition at202.1° C. which may be a glass transition temperature. Thehomopolytriazine recovered from the DSC analysis was a transparent,light amber colored, rigid solid.

Example 3 Synthesis and Recrystallization to Produce High Purity1,1-Bis(4-cyanatophenyl)cyclododecane

The synthesis of 1,1-bis(4-cyanatophenyl)cyclododecane of Example 1 wasrepeated, but with a 2-fold increase in scale. The 38.86 grams ofrecovered product assayed 0.69 area percent unreacted1,1-bis(4-hydroxyphenyl)cyclododecane, 3.91 area % monocyanate, and95.40 area % dicyanate by HPLC analysis. Recrystallization was performedby forming a solution in boiling acetone (50 milliliters), then holdingfor 24 hours at 23° C. The acetone solution was removed from thecrystalline product via decantation. HPLC analysis of a portion of thedamp crystalline product revealed the presence of no detectableunreacted 1,1-bis(4-hydroxyphenyl)cyclododecane, 1.02 area %monocyanate, and 98.98 area % dicyanate. A second recrystallization ofthe damp crystalline product from acetone (40 milliliters) followed bydrying in the vacuum oven at 50° C. for 48 hours provided 20.12 grams ofbrilliant white product with no detectable unreacted1,1-bis(4-hydroxyphenyl)cyclododecane, 0.42 area % monocyanate, and99.58 area % dicyanate by HPLC analysis. Combination of the acetonesolution decants from the two recrystallizations followed byconcentration of the solution to a volume of 28 milliliters yielded asecond crop of brilliant white product (8.39 grams) with a trace(non-integratable) of unreacted 1,1-bis(4-hydroxyphenyl)cyclododecane,2.28 area % monocyanate, and 97.72 area % dicyanate by HPLC analysis.

Reference Example 1 Synthesis of the Bis(Allyl Ether) of1,1-Bis(4-hydroxyphenyl)cyclododecane

Allyl alcohol (101.58 grams, 1.75 moles), dimethyl carbonate (157.55grams, 1.75 moles), and sodium methoxide catalyst (0.18 gram, 0.065percent by weight) were added to a 500 milliliter, 3 neck, round bottomglass reactor and maintained at room temperature (23° C.) with stirringunder a nitrogen atmosphere. The reactor was additionally outfitted witha chilled condenser, a thermometer, magnetic stirring, and athermostatically controlled heating mantle. An equilibrium mixture ofallylmethyl carbonate, diallyl carbonate, and methanol was rapidlyformed concurrent with cooling of the reactor contents to 15.5° C. After13 minutes 1,1-bis(4-hydroxyphenyl)cyclododecane (28.31 grams, 0.1606equivalent of hydroxy groups), was added to the reactor followed by amixture of triphenylphosphine (0.56 gram, 0.204 percent by weight) and5% palladium on carbon (0.38 gram, 0.127 percent by weight). The1,1-bis(4-hydroxyphenyl)cyclododecane assayed 99.76 area % via highpressure liquid chromatographic (HPLC) analysis with the balanceconsisting of 2 minor components (0.09 and 0.15 area %). Heatingcommenced and over the next 127 minutes the reaction temperature reached79-80° C. The reaction mixture was maintained for 8 hours at 77.5-80° C.and then cooled to room temperature and vacuum filtered through a bed ofdiatomaceous earth packed on a medium fritted glass funnel. Therecovered filtrate was rotary evaporated at a maximum oil bathtemperature of 100° C. and to a vacuum of 1.7 mm Hg pressure to providea transparent, light yellow colored, liquid (35.04 grams) which became atacky solid at room temperature.

HPLC analysis revealed the presence of 96.78 area % allyl ether of1,1-bis(4-hydroxyphenyl)cyclododecane with the balance as a single minorcomponent (3.22 area %). The single minor component was removed bydissolving the product in dichloromethane (100 milliliters) and passingthe resultant solution through a 2 inch deep by 1.75 inch diameter bedof silica gel (230-400 mesh particle size, 60 angstrom mean pore size,550 m²/gram surface dimension) supported on a medium fritted glassfunnel. After elution from the silica gel bed with additionaldichloromethane, a yellow band remained in the region of the origin.Rotary evaporation provided 33.98 grams (98.94% isolated yield) of paleyellow colored tacky solid.

HPLC analysis revealed the presence of 99.57 area % allyl ether of1,1-bis(4-hydroxyphenyl)cyclododecane with the balance as 2 minorcomponents (0.22 and 0.21 area %). Infrared spectrophotometric analysisof a film sample of the product on a KBr plate revealed peaks in therange expected for unsaturated C—H stretch (3032, 3058, 3081 cm ⁻¹),saturated C—H stretch (2862, 2934 cm [shoulder present on both]), C═Cstretch (1581, 1607 cm⁻¹), C—O stretch (1026 cm⁻¹), and CH═CH₂deformation (924, 998 cm⁻¹), accompanied by total absence of hydroxylgroup absorbance thus confirming full conversion of the phenolichydroxyl groups to allyl ether groups.

Example 4 Thermally Induced Copolymerization of Bis(Allyl Ether) of1,1-Bis(4-hydroxyphenyl)cyclododecane (25% wt.) and1,1-Bis(4-cyanatophenyl)cyclododecane (75% wt.)

1,1-Bis(4-cyanatophenyl)cyclododecane (0.5034 gram, 75% wt.) andbis(allyl ether) of 1,1-bis(4-hydroxyphenyl)cyclododecane (0.1678 gram,25% wt.) from Reference Example 1 were weighed into a glass vial towhich dichloromethane (1 5 milliliters) was added. HPLC analysis of the1,1-bis(4-cyanatophenyl)cyclododecane revealed 99.44 area % dicyanate,and 0.56 area % monocyanate. Shaking the vial provided a solution whichwas added to an aluminum tray. Devolatilization conducted in a vacuumoven at 40° C. for 30 minutes removed the dichloromethane, giving ahomogeneous blend. DSC analysis of portions (9.70 and 10.00 milligrams)of the blend was conducted using a rate of heating of 5° C. per minutefrom 25° C. to 400° C. under a stream of nitrogen flowing at 35 cubiccentimeters per minute.

An endotherm was observed with an average 99.0° C. onset (98.07 and99.96° C.), 118.8° C. minimum (118.72 and 118.93° C.), and 126.5° C.endpoint (124.61 and 128.40° C.), accompanied by an enthalpy of 11.5joules per gram (10.13 and 12.76 joules per gram) (individual values inparenthesis). An exotherm attributed to copolymerization of the allyland cyanate groups (plus any homopolymerization) was observed with anaverage 172.2° C. onset (170.58° C. and 173.90° C.), 249.1° C. maximum(248.30° C. and 249.80° C.), and 292.92° C. endpoint (289.54° C. and296.18° C.) accompanied by an enthalpy of 487.1 joules per gram (474.9and 499.2 joules per gram) (individual values in parenthesis). Thecopolymer recovered from the DSC analysis was a transparent, ambercolored, rigid solid.

Example 5 Glass Transition Temperature of Copolymer of Bis(Allyl Ether)of 1,1-Bis(4-hydroxyphenyl)cyclododecane (25% wt.) and Dicyanate ofCyclododecane Bisphenol (75% wt.)

Curing of the remaining blend from Example 4 was completed in an ovenusing the following curing schedule: 150° C. for 1 hour, 200° C. for 1hour, 250° C. for 1 hour. DSC analysis of portions (28.2 and 35.0milligrams) of the cured product gave an average glass transitiontemperature of 214.3° C. (212.85° C. and 215.83° C.) (individual valuesin parenthesis).

Example 6 Thermally Induced Copolymerization of Bis(Allyl Ether) of1,1-Bis(4-hydroxyphenyl)cyclododecane (50% wt.) and1,1-Bis(4-cyanatophenyl)cyclododecane (50% wt.)

1,1-Bis(4-cyanatophenyl)cyclododecane (0.2978 gram, 50% wt.) andbis(allyl ether) of 1,1-bis(4-hydroxyphenyl)cyclododecane (0.2978 gram,50% wt.) from Reference Example 1 were weighed into a glass vial towhich dichloromethane (1.5 milliliters) was added. HPLC analysis of the1,1-bis(4-cyanatophenyl)cyclododecane revealed 99.44 area % dicyanateand 0.56 area % monocyanate. Shaking the vial provided a solution whichwas added to an aluminum tray. Devolatilization conducted in a vacuumoven at 40° C. for 30 minutes removed the dichloromethane, giving ahomogeneous blend.

DSC analysis of portions (9.70 and 10.70 milligrams) of the blend wasconducted using a rate of heating of 5° C. per minute from 25° C. to400° C. under a stream of nitrogen flowing at 35 cubic centimeters perminute. No endotherm was observed. An exotherm attributed tocopolymerization of the allyl and cyanate groups (plus anyhomopolymerization) was observed with an average 173.7° C. onset(171.05° C. and 176.27° C.), 246.5° C. maximum (245.96° C. and 247.01°C.), and 282.0° C. endpoint (281.01° C. and 282.91° C.), accompanied byan enthalpy of 414.2 joules per gram (403.2 and 425.1 joules per gram)(individual values in parenthesis). The copolymer recovered from the DSCanalysis was a transparent, amber colored, rigid solid.

Example 7 Glass Transition Temperature of Copolymer of Bis(Allyl Ether)of 1,1-Bis(4-hydroxyphenyl)cyclododecane (50% wt.) and1,1-Bis(4-cyanatophenyl)cyclododecane (50% wt.)

Curing of the remaining blend from Example 6 was conducted in an ovenusing the following curing schedule: 150° C. for 1 hour, 200° C. for 1hour, 250° C. for 1 hour. DSC analysis of portions (33.8 and 34.3milligrams) of the cured product gave residual exothermicity at >260° C.After a second scanning an average glass transition temperature of144.57° C. (140.98° C. and 148.15° C.) (individual values inparenthesis) was measured. A third scanning was completed since residualexothermicity was observed at >330° C. An average glass transitiontemperature of 160.03° C. (159.52° C. and 160.53° C.) with no residualexothermicity observed.

Example 8 Copolymerization of Bis(Allyl Ether) of1,1-Bis(4-hydroxyphenyl)cyclododecane (25% wt.) and1,1-Bis(4-cyanatophenyl)cyclododecane (75% wt.) Using Catalyst

1,1-Bis(4-cyanatophenyl)cyclododecane (0.7709 gram, 75% wt.), bis(allylether) of 1,1-bis(4-hydroxyphenyl)cyclododecane (0.2570 gram, 25% wt.)from Reference Example 1, and 6% cobalt naphthenate (0.0051 gram, 0.5%wt.) were weighed into a glass vial to which dichloromethane (1.5milliliters) was added. HPLC analysis of the1,1-bis(4-cyanatophenyl)cyclododecane revealed 99.44 area % dicyanateand 0.56 area % monocyanate. Shaking the vial provided a solution whichwas added to an aluminum tray. Devolatilization conducted in a ventedoven at 40° C. for 30 minutes removed the dichloromethane, giving ahomogeneous blend.

DSC analysis of portions (10.1 and 12.5 milligrams) of the blend wasconducted using a rate of heating of 5° C. per minute from 25° C. to400° C. under a stream of nitrogen flowing at 35 cubic centimeters perminute. An endotherm was observed with an average 51.62° C. onset(41.67° C. and 61.57° C.), 85.29° C. minimum (79.93° C. and 90.64° C),and 93.09° C. endpoint (90.48° C. and 95.70° C.) accompanied by anenthalpy of 16.22 joules per gram (8.65 and 23.79 joules per gram)(individual values in parenthesis). An exotherm attributed to acopolymerization of the allyl and cyanate groups (plus anyhomopolymerization) was observed with an average 93.09° C. onset (90.48°C. and 95.70° C.), 162.04° C. and 238.36° C. maxima that merged together(161.28° C., 162.79° C., 236.93° C., and 239.78° C.), and 283.38° C.endpoint (282.43° C. and 284.33° C.) accompanied by an enthalpy of 422.6joules per gram (413.0 and 432.1 joules per gram) (individual values inparenthesis). The copolymer recovered from the DSC analysis was atransparent, amber colored, rigid solid.

Example 9 Thermogravimetric Analysis (TGA) and Differential ScanningCalorimetry (DSC) of Copolymer of Bis(Allyl Ether) of1,1-Bis(4-hydroxyphenyl)cyclododecane (25% wt.) and1,1-Bis(4-cyanatophenyl)cyclododecane (75% wt.) Prepared Using Catalyst

1,1-Bis(4-cyanatophenyl)cyclododecane (3.00 grams, 75% wt.), bis(allylether) of 1,1-bis(4-hydroxyphenyl)cyclododecane (1.00 gram, 25% wt.)from Reference Example 1, and 6% cobalt naphthenate (0.0040 gram, 0.1%wt.) were weighed into a glass vial to which dichloromethane (2.0milliliters) was added. HPLC analysis of the dicyanate of cyclododecanebisphenol revealed 99.44 area % dicyanate and 0.56 area % monocyanate.Shaking the vial provided a solution which was added to a round aluminumpan. Devolatilization conducted in a vacuum oven at 50° C. for 30minutes removed the dichloromethane giving a homogeneous blend. Curingwas conducted in ovens using the following curing schedule: 100° C. for1 hour, 150° C. for 1 hour, 200° C. for 2 hours, 250° C. for 1 hour. Arigid, transparent, amber colored disk was recovered after curing anddemolding from the aluminum pan.

DSC analysis of portions (33.0 and 34.3 milligrams) of the cured productwas conducted using a rate of heating of 5° C. per minute from 25° C. to400° C. under a stream of nitrogen flowing at 35 cubic centimeters perminute. Residual exothermicity was observed at >260° C. and an averageglass transition temperature of 181.83° C. (185.80° C. and 177.85° C.)(individual values in parenthesis) was measured. TGA of a portion(20.3110 milligrams) of the cured product was conducted using a rate ofheating of 10° C. per minute from 25° C. to 600° C. under a dynamicnitrogen atmosphere. A step transition with an onset temperature of400.42° C. and an end temperature of 446.57° C. was observed. Thetemperatures at 99.00, 95.00 and 90.00% of original sample weight were243.23° C., 373.76° C. and 396.76° C., respectively.

Example 10 Moisture Resistance of Copolymer of Bis(Allyl Ether) of1,1-Bis(4-hydroxyphenyl)cyclododecane (25% wt.) and1,1-Bis(4-cyanatophenyl)cyclododecane (75% wt.) Prepared Using Catalyst

The remaining portion of the cured copolymer disk from Example 9 wasweighed, added to a 4 ounce glass jar along with deionized water (40milliliters), sealed and then placed in an oven maintained at 55° C. Thedisk was removed at the indicated intervals, blotted dry, weighed, andthen replaced back into the sealed jar for continuation of the testing.The change in weight from the original was calculated for each timeinterval, providing the following results given in the table.

Exposure to Deionized Water at 55° C. Duration of Exposure Copolymer ofExample 10 (hours) (% wt. increase) 9.0 0.573 25.33 0.768 51.83 0.85995.16 1.055 119.08 1.081 143.00 1.068 167.17 1.081

Reference Example 2 Synthesis and Characterization of the Tetraphenol ofDimethylcyclohexane

Phenol (598 g, 6.36 moles) and cyclohexane dicarboxaldehyde (74.2 g,0.53 moles, mixture of 1,3- and 1,4-isomers; ratio of phenolic groups toaldehyde groups=6:1, equivalent ratio of phenol to cyclohexanedicarboxaldehyde=3:1) were added together in a 1-L 5-neck reactor. Themixture was heated to 50° C. with 500 rpm mechanical stirrer agitation.At 50° C. and atmospheric pressure, p-toluenesulfonic acid (PTSA)(1.3959 g total, 0.207% by weight) was added in six portions over 30minutes. The temperature increased a few degrees with each PTSAaddition. After the 6th PTSA addition, the temperature controller wasset to 70° C. and vacuum was applied to the reactor. In order to avoidthe reactor content flooding the rectifier, the reactor pressure wasgradually decreased to remove water from the reaction solution. When thereflux had stopped, the reactor was vented and water (48 g) was added.

Water (79 g) and NaHCO₃ (0.6212 g) were added to neutralize the PTSA.When the reaction contents had cooled to room temperature, the entirecontents were transferred to a 2-L separatory funnel. Methyl ethylketone (MEK) was added, and the contents were washed several times withwater to remove PTSA-salt. The solvents and excess phenol were removedusing a rotary evaporator, and the hot novolac was poured onto aluminumfoil. The reaction of phenol with cyclohexane dicarboxaldehyde producedas the predominant product a tetraphenol possessing the followingidealized structure (tetraphenol of dimethylcyclohexane):

Ultraviolet spectrophotometric analysis provided a hydroxyl equivalentweight (HEW) of 118.64. High pressure liquid chromatographic (HPLC)analysis was adjusted to resolve 24 (isomeric) components present in theproduct.

Although the present invention has been described in considerable detailwith regard to certain versions thereof, other versions are possible,and alterations, permutations, and equivalents of the version shown willbecome apparent to those skilled in the art upon a reading of thespecification and study of the drawings. Also, the various features ofthe versions herein can be combined in various ways to provideadditional versions of the present invention. Furthermore, certainterminology has been used for the purposes of descriptive clarity, andnot to limit the present invention. Therefore, any appended claimsshould not be limited to the description of the preferred versionscontained herein and should include all such alterations, permutations,and equivalents as fall within the true spirit and scope of the presentinvention.

Having now fully described this invention, it will be understood tothose of ordinary skill in the art that the methods of the presentinvention can be carried out with a wide and equivalent range ofconditions, formulations, and other parameters without departing fromthe scope of the invention or any embodiments thereof.

1. A dicyanate compound of formula (I):

wherein: each m independently is 0, 1, or 2; the moieties R^(a) andR^(b) independently represent optionally substituted aliphatic groupscomprising a total of from about 5 to about 24 carbon atoms and R^(a)and R^(b) together with the carbon atom to which they are bonded mayform an optionally substituted and/or optionally unsaturated and/oroptionally polycyclic aliphatic ring structure which has at least about8 ring carbon atoms; and the moieties R independently represent halogen,cyano, nitro, optionally substituted alkyl, optionally substitutedcycloalkyl, optionally substituted alkoxy, optionally substitutedalkenyl, optionally substituted alkenyloxy, optionally substituted arylhaving from 6 to about 10 carbon atoms, optionally substituted aralkylhaving from 7 to about 12 carbon atoms, optionally substituted aryloxyhaving from 6 to about 10 carbon atoms, and optionally substitutedaralkoxy having from 7 to about 12 carbon atoms.
 2. The dicyanatecompound of claim 1, wherein the dicyanate is of formula (Ia):

wherein: m and R are as defined in claim 1; and n has a value of fromabout 7 to about 24; and any non-aromatic cyclic moieties comprised inthe above formula (Ia) may optionally carry one or more substituentsand/or may optionally comprise one or more double bonds and/or mayoptionally be polycyclic.
 3. The dicyanate compound of claim 1, whereinn has a value of from about 9 to about
 16. 4. The dicyanate compound ofclaim 1, wherein n has a value of 10, 11, or
 12. 5. The dicyanatecompound of claim 1, wherein n equals
 11. 6. The dicyanate compound ofclaim 1, wherein each m independently is 0 or
 1. 7. The dicyanatecompound of claim 1, chosen from 1,1-bis(4-cyanatophenyl)cyclododecane,1,1-bis(4-cyanato-3,5-dimethylphenyl)cyclo-dodecane,1,1-bis(4-cyanato-3-methylphenyl)cyclododecane,1,1-bis(4-cyanatophenyl)cyclodecane,2,2-bis(4-cyanatophenyl)adamantanone,4,4′-bis(4-cyanatophenyl)octahydro-1,4:5,8-dimethanonaphthalen-2(1H)ylideneand 5,5-bis(4-cyanatophenyl)hexahydro-4,7-methanoindane.
 8. Thedicyanate compound of claim 1, which is1,1-bis(4-cyanatophenyl)cyclododecane.
 9. A polymer or prepolymer of adicyanate of claim
 1. 10. A polymerizable mixture, wherein the mixturecomprises at least one dicyanate compound of claim 1 and/or a prepolymerthereof, and one or more substances which are selected frompolymerization catalysts, co-curing agents, flame retardants, synergistsfor flame retardants, solvents, fillers, glass fibers, adhesionpromoters, wetting aids, dispersing aids, surface modifiers,thermoplastic polymers, and mold release agents.
 11. A polymerizablemixture, wherein the mixture comprises at least (i) at least onedicyanate compound of claim 1 and/or a prepolymer thereof and (ii) atleast one compound and/or a prepolymer thereof which is capable ofreacting with (i).
 12. The mixture of claim 11, wherein the at least onecompound (ii) is selected from compounds which comprise one or morepolymerizable ethylenically unsaturated moieties, aromatic di- andpolycyanates which are different from a dicyanate compound of formula(I), aromatic di- and polycyanamides, di- and polymaleimides, and di-and polyglycidyl ethers.
 13. The mixture of claim 11, wherein themixture further comprises one or more substances which are selected frompolymerization catalysts, co-curing agents, flame retardants, synergistsfor flame retardants, solvents, fillers, glass fibers, adhesionpromoters, wetting aids, dispersing aids, surface modifiers,thermoplastic polymers, and mold release agents.
 14. The mixture ofclaim 10, wherein the mixture is partially or completely polymerized.15. A product which comprises a polymerized mixture of claim
 10. 16. Theproduct of claim 15, wherein the product is at least one of anelectrical laminate, an IC substrate, a casting, a coating, a die attachand mold compound formulation, a composite, and an adhesive.
 17. Aprocess for preparing the dicyanate compound of claim 1, wherein theprocess comprises reacting a compound of formula (II):

wherein m, R^(a), R^(b) and R are as set forth in claim 1 in a solventwith an at least about stoichiometric quantity of a cyanogen halide inthe presence of an at least about stoichiometric quantity of a base. 18.The process of claim 17, wherein the cyanogen halide comprises at leastone of cyanogen chloride and cyanogen bromide.
 19. The process of claim17, wherein the reaction is carried out at a temperature of from about−40° C. to about 60° C.
 20. The process of claim 17, wherein the basecomprises one or more of sodium hydroxide, potassium hydroxide,trimethylamine, and triethylamine.
 21. The process of claim 17, whereinthe base comprises triethylamine.
 22. The process of claim 17, whereinthe solvent comprises one or more of water, an aliphatic ketone, achlorinated hydrocarbon, an aliphatic or cycloaliphatic ether ordiether, and an aromatic hydrocarbon.
 23. The process of claim 17,wherein the solvent comprises one or more of acetone, methylethylketone,methylene chloride, and chloroform.